Glyceridic oil compositions and processes of preparing them



Patented Oct. 25, 1949 UNITED STATES PATENT OFFICE GLYCERIDIC on. comrosrrrons AND rnocassas or raamamc mam No Drawing. Application December 4, 1948, Serial No. 63.628

16 Claims. .1

This application is a continuation-in-part of the applications S. N. 608,101, filed July 31, 1945, S. N. 608,102, flied July 31, 1945, S. N. 608,380, filed August 1, 1945 and S. N. 747,848, filed May 13, 1947.

This invention relates to glyceridic oil compositions.

An object of this invention is to extend the utility of cooking and baking fats by increasing the ease with which they may be employed for different cooking and baking purposes.

Another object of this invention is to provide shortening which, when utilized as a component in baking, results in improved baked products.

Another obi ect of this invention is to extend the range of utility of cooking and baking fats by increasing the ease with which they may be employed in a wide variety of culinary uses.

While glyceridic fats employed for cooking and baking without the addition of any modifying agent are satisfactory for some purposes, they fall far short when utilized as a component in the preparation of certain baked goods. For examle, if it is desired to produce a white cake containing more sugar than flour, a glyceridic fat or shortening containing no modifying agent results in an unsatisfactory product. Again, if an unmodified shortening is employed as an ingredient in baking, the batter under certain conditions will be a loose emulsion having a grainy and curdy appearance. Generally, for baked products, the

following criteria represent a good shortening for baking purposes:

1. The batter obtained by mixing the shortening with other ingredients of the baked goods should be a tight emulsion which has a. smooth and syrupy appearance.

2. The batter should be relatively easy to prepare with a minimum of mixing.

3. The finished baked product should have good eating qualities, 1. e., it should be tender, soft, possess a desirable flavor, be readily dispersibie in the mouth and have a good grain structure.

4. The finished baked product should be of pleasing appearance, have firmness and fineness of grain, and in particular. have the desired volume.

In accordance with this invention, glyceridic oil compositions are provided-which fulfill all of the desired criteria for shortening and other uses and which contain relatively small total quantities of modifying agents. The shortening compositions of this invention are prepared by incorporating in a glyceridic oil a mixture of mono-aikyl, dialkyl and tri-alkyl citrates in which the alkyl group has at least 14 carbon atoms, and pref erably at least 16 carbon atoms. or a mixture of mono-alkyiene citrate, di-alkylene citrate and tri-alkylene citrate in which the alkyiene roup has at least 14 carbon atoms, and preferably at least 18 carbon atoms. For some purposes, the mixture of alkyiene citrates in the giyceridic oil composition is unsatisfactory from a taste standpoint. The amounts of mono-ester, di-ester and tri-ester of citric acid in the Blyceridic oil or fat composition are a, to and preferably 1*; to of the mono-ester of citric acid. 1: .to 154%, and preferably V; to of the di-ester of citric acid, and Ya to 1%%. and preferably V9 to of the tri-ester of citric acid. The mixture of citrates incorporated in the glyceridic oil may be of one alkyl or alkyiene specie or a plurality of such species. For example, the mixture may contain mono-stearyl citrate, mono-oleyi citrate, di-stearyi citrate, di-oleyl citrate, tri-stearyl citrate, tri-oleyl citrate and stearyl-oleyl citrates. However, the total amount of mono-esters of citric acid, whether mono-alkyl citrates or monoalkyiene citrates or both, should be within the range of I}, to and preferably to /4%. Likewise, the amounts of di-esters of citric acid and tri-esters of citric acid should be respectivey 1; to 1'/z% and preferably V to /z% of the di-esters, and V to i'/4% and preferably ,4; to i/2% of the tri-esters. It is essential that the mono-, diand tri-esters of citric acid each be present in the glyceridic oil composition in order to obtain the new results achieved by the practice of this invention.

While the presence of the mono-alkyi citrate or mono-alkyiene citrate in which the alkyl group has at least 14 carbon atoms. and preferably at least 16 carbon atoms, materially retards the rancldity of the glyceridic oil composition, retardation of rancidity is sometimes more easily achieved by incorporating in the glyceridic fat composition immediately after deodorization, 0.002 to 0.1% of a mono-alkyl citrate in which the alkyl group has not more than 12 carbon glyceridic fat composition to obtain a given deagent and to add the resulting solution to the glyceridic oil. By the use of such coupling agents or dispersing agents, the lower molecular weight. citrates are dispersed throughout the glyceridic" oil. This addition to the glyceridic oil of the mono-alkyl citrate in which the alkyl group has not more than 12 carbon atoms or of the monoalkylene citrate in which the alkylene group has not more than 12 carbon atoms is made immediately after deodorization.

In addition to the mixture of the alkyl or alkylene citrates in which the alkyl or alkylene group has at least 14 carbon atoms, and preferably at least 16- carbon atoms, a hydrophilic lipin containing at least one aliphatic hydrocarbon group having at least 13 carbon atoms, and

preferably not more than 21 carbon atoms, is desirably incorporated in the glyceridic oil composition. For example, it has been found advantageous to incorporate in the glyceridic 011 composition to 2%%, and preferably 1 to 2%, by

weight of aliphatic mono-carboxylic acid monoesters of glycerol in which the mono-carboxylic acid residue has at least 14, and preferably at least 16, carbon atoms. Desirably, when a monocarboxylic acid mono-ester of glycerol is incorporated in the oil in addition to the mixture of alkyl or alkylene citrates, the ratio by weight oi. total citrates to the mono-esters of glycerol in the oil is about 2 to 3. Again, a very satisfactory shortening composition is produced by incorporating in the composition containing the mixed citrates 1 to 6%, and preferably 2 to 4%, of a mono-hydric alkyl' or alkylene alcohol having at least 14, and preferably at least 16 carbon atoms. Other hydrophilic lipins usable for this purpose are aliphatic mono-carboxylic acid di-esters of glycerol in which the mono-carboxylic acid residue has at least 14, and preferably at least 16 carbon atoms and the partial esters of propylene glycol, di-propylene glycol, di-glycerol, poly-glycerols, hydroxy-methyl glycerols, sorbitol, hydroxy ethyl sorbitols, sorbitans, mannitols, mannitans, glucose, methyl glucoside and erythritol.

If it is desired to employ both .an aliphatic mono-carboxylic acid mono-ester of glycerol in which the mono-carboxylic acid residue has at least 14 carbon atoms and the monohydric alcohol having at least 14 carbon atoms in addition to the mixture of citrates, a satisfactory glyceridic oil composition is produced by incorporating in it, in addition to the mixture of citrates, to 154% of the aliphatic monocarboxylic acid mono-esters and ,5 to 3% of the mono-hydric alcohol.

It issometimes advantageous to incorporate 70 in the glyceridic oil composition with the mixture of citratesand with or without the hydrophilic lipin containing at least one hydro-carbon group having from 13 to 21 carbon atoms, M; to 1% With lower molecular weight mono- 10 soya bean lecithin or corn lecithin. These commercial vegetable phosphatides contain about 55 to of total phosphatides. The amount of phosphorus as phosphatides in these commercial vegetable phophatides is 2.2 to 2.5%.

Since the mono-alkyl, di-alkyl and trl-alkyl citrates or the mono-alkylene, di-alkylene and tri-alkylene citrates are desirably all incorporated in the glyceridic oil, it is advantageous to prepare a mixture of all three esters simultaneously. The mixture-of mono-, diand tri-esters of citric acid may be prepared by the esteriflcation of citric acid and an alcohol, such as an alkyl or alkylene primary or secondary alcohol, preferably by reacting the citric acid and the alcohol in proportions which favor the formation of the mono-, diand tri-esters of citric acid in the ratio desired in the mixture. The esteriiication may be conducted by any of the well-known methods employedv for the production oi esters and the mono-, diand tri-esters in the resulting reaction mixture may, if desired, be separated from each other by any suitable method, such as fractional crystallization or selective extraction with a suitable solvent. However, for most purposes, the reaction product may be used as such if it contains the mono-, diand tri-esters of citric acid in the proportions desired in the mixture.

Examples of the mono-, diand tri-alkyl or alkylene citrates comprising the mixture which is incorporated in the glyceridic oil are the citric acid esters of the following alcohols: tetradecanols, tetradecenols, hexadecanols. hexadecenols,- octadecanols, octadecenols, dicosanols, dicosenols, docosanols and doccsenols.

Examples of the mono-alkyl citrate in which the alkyl group has not more than 12 carbon atoms and mono-alkylene citrate in which the alkylene group has not more than 12 carbon atoms are the citric acid esters of methanol. ethanol, propanols, propenols, hexanols, hexenols, octanols and octenols.

Examples of aliphatic mono-carboxylic acid mono-esters of glycerol which may be incorporated in the glyceridic oil are the mono-esters of glycerol of the following fatty acids: myristic, palmitic and stearic acids.

Examples of the mono-hydric alkyl or alkylene alcohols which are used as the hydrophilic lipin are ste'aryl alcohol, oleyl alcohol, cetyl alcohol and myristyl alcohol.

Most of the hydrophilic lipins employed in the practice of this invention may also be employed as the solubilizing or dispersing aid for the monoalkyl citrate in which the mono-alkyl group has not more than 12 carbon atoms or mono-alkylene citrate in which the alkylene group has not more than 12 carbon atoms. For example, the aliphatic mono-carboxylic acid mono-esters of glycerol in which the mono-carboxylic acid residue has at least 14, and preferably at least 16, carbon atoms or the mono-hydric alcohols having at least 14, and preferably at least 16, carbon atoms are well suited for the purpose. Accordingly, if the solubilizing agent or dispersing aid for the lower mono-esters of citric acid is one of the hydrophilic lipins employed in the practice of this invention, the quantity of such hydrophilic lipin used as the solubilizing agent should, of course, be included in the calculation of the total hydrophilic lipin in the glyceridic oil composition.

Examples of solubilizing agents, other than the hydrophilic lipins, which may be employed are oleic.

of commercial vegetable phosphatides, such as 15 mono-carboxylic acids having at least 10 carbon invention is obtained by reference to the following examples:

Example 1.Shortening containing mono-stearyl citrate, di-s-tearyl citrate, tri-stearyl citrate and mono-glycerides of fatty acids A shortening particularly adapted for use in baked products containing a ratio of sugar greater than 1 to 1, such as 1.4 to 1, is produced by incorporating in the shortening about 0.15% of mono-stearyl citrate, 0.5% of di-stearyl' citrate, 0.35% of tri-stearyl citrate and 1 of the 'mono-glycerides obtained from the fat of the shortening. A mixture of 50% cottonseed oil, 30% cottonseed stearin and 20% peanut oil is hydrogenated and deodorlzed to produce a shortening composition.

To 5 kilograms of the mixed hydrogenated oils are added 150 grams of a mixture of the monoand di-glycerides prepared from the mixture of oils. The monoand di-glycerides, are prepared from the mixture of oil by reacting glycerin with the oil in the presence of sodium bicarbonate. The amounts of oil and glycerin added are such as to produce a mixture of about 50% monoglycerides and about 50% di-glycerides. This mixture of monoand di-glycerides is added at a temperature of about 35 to 50 C. to the main body of the mixture of hydrogenated oils. 50 grams of a mixture of mono-stearyl citrate, distearyl citrate and tri-stearyl citrate are also added to the main body of hydrogenated oil, preferably by initially dissolving them in a small quantity of the oil which is heated to a temperature of about 60 C. and adding the resulting solution to the main body of the oil. The mono-stearyl, di-stearyl and tri-stearyl citrates contain about 15% mono-stearyl citrate, 50% di-stearyl citrate and 35% trl-stearyl citrate.

The mixture of mono-stearyl citrate, di-stearyl citrate and tri-stearyl citrate is prepared as follows:

12.1 kilograms of citric acid mono-hydrate are added to 30 kilograms of commercial stearyl alcohol which is previously melted. During the addition, the mixture is agitated. The mixture is held at 150 C. under reduced pressure for a period of 1 /2 hours. At the end of this period, boiling and foaming ceases substantially. The resulting product which consists of a mixture of mono-stearyl citrate, di-stearyl citrate and tri-stearyl citrate has an acid value of about 83, a saponification value of about 249.0 and a melting point of about 51-68 C. and a color on the Lovibond scale of about 36Y-5.8R.

Example 2.Shorten2'ng composition containing mono-stearyl citrate, (ti-stearyl citrate and tri-stearyl citrate A shortening composition adapted for use in the preparation of baked products having relatively low sugar content produced by incorporating in a shortening consisting of about 25% soya bean oil and the balance cottonseed oil which are both hydrogenated and deodorized, 0.15% of mono-stearyl citrate, 0.5% of di-stearyl citrate and 0.35% of tri-stearyl citrate. Alternately, a

'good shortening is produced by doubling the quantity of the stearyl citrates so that the resulting shortening contains 0.3% mono-stearyl citrate, 1.0% of di-stearyl citrate and 0.7% of tri-stearyl citrate. The mono-stearyl citrate, di-

stearyl citrate and trl-stearyl citrate may be prepared as described in Example 1, and the mixture of stearyl citrates is preferably added to the oil by initially dissolving the mixture in a small quantity of the oil at a temperature of .about 60 C. and adding the resulting solution to the main body of the 011.

Example 3.-Shortening containing mono-stearyl citrate, di-stearyl citrate, tri-stearyl citrate and stearyl alcohol To 5 kilograms of a hydrogenated and deodorized 011 containing 60% peanut oil and 40% cottonseed oil are added 200 grams of stearyl alcohol and 50 grams of a mixture of stearyl citrates containing 15% of mono-stearyl citrate, 50% di-stearyl citrate and 35% of tri-stearyl citrate. Deslrably. the mixture of stearyl citrates, which is prepared in accordance with the method described in Example 1, is dissolved in a small quantity of the oil at' a temperature of 60 C. and the resulting solution added to the main body of the oil.

Desirably, 1.25 grams of mono-isopropyl citrate are incorporated in the hydrogenated oil immediately after deodorization. If the mono-isopropyl citrate is incorporated in the oil, it can conveniently be added by dissolving it in the stearyl alcohol prior to the addition of that substance to the main body of the oil.

The mono-isopropyl citrate is prepared as follows:

260 grams of anhydrous citric acid are mixed with grams of commercial isopropyl alcohol, and the mixture is heated at 155 C. for 2 hours in a closed vessel. The pressure developed by the alcohol corresponds to about 55 lbs. per square inch. The alcohol is then evaporated under reduced pressure with a nitrogen stream at 130 C. A typical acid value of the resulting product is 386. and a typical saponiflcation number 702. A typical ratio of free carboxyl to total carboxyl Pure mono-isopropyl citrate may be obtained from this preparation by causing it to precipitate from ethyl ether solutions by the addition of petroleum ether.

Example 4.Sh0rtening containing mono-myristyl citrate, di-myristyl citrate, tri-myristyl citrate and mono-glycerides of fatty acid To 5 kilograms of a mixture of hydrogenated and deodorized oils consisting of about 35% soya bean oil and about 65% cottonseed oil are added grams of a mixture of the monoand diglycerides prepared from the mixture of the hydrogenated oils and 100 grams of a mixture of a mono-myristyl citrate, di-myristyl citrate and tri-myristyl citrate containing about 20% monomyristyl citrate, 50% cli-myristyl citrate and 30% 'tri-myristyl citrate. The mixture of monoand di-glycerides which contains about 50% of the mono-glycerides and about 50% of the diglycerides was prepared from the mixture of hydrogenated soya bean and cottonseed oils in the same manner as the monoand di-glycerides were produced as described in Example 1. The mixture of mono-myristyl citrate, di-myristyl citrate and tri-myristyl citrate was initially dissolved in a small quantity of the mixture of hydrogenated soya bean and cottonseed oil and heated to 60 C. prior to addition to the main body of the oil.

The mixture of mono-myristyl citrate, di-myristyl citrate and trim-myristyl citrate was prepared as follows:

31 kilograms of anhydrous citric acid are added to 69 kilograms of commercial myristyl alcohol which is previously melted. During the addition, the mixture is agitated. The mixture is heated at 150 C. under reduced pressure for a period of 1 hours and at the end of this period boiling and foaming ceases substantially. The resulting product which consists of monomyristyl citrate, di-myristyl citrate and trimyristyl citrate has an acid value of about 99 and a saponiflcation value of about 291.

Example 5.-Shortening containing mono-olepl citrate, di-oleyl citrate, tri-oleul citrate and mono-glycerides of fatty acid To 5 kilograms of a hydrogenated and deodorrized lard are added 150 grams of a mixture of the monoand di-glycerides prepared from the lard and 25 grams of a mixture of mono-oleylcitrate, di-oleyl citrate and tri-oleyl citrate. The mixture of monoand di-glycerides of the lard is prepared in the same manner as described for the monoand di-glycerides in Example 1, except that hydrogenated lard is employed instead of the mixture of oils described in that example. The mixture of mono-oleyl citrate, di-oleyl citrate and tri-oleyl citrate which contains about 20% mono-oleyl citrate, 60% di-oleyl citrate and 20% tri-oleyl citrate is added directly to the oil.

The mixture of mono-oleyl citrate, di-oleyl citrate and tri-oleyl citrate is prepared as follows:

12.1 kilograms of citric acid mono-hydrate are added to 30 kilograms of commercial oleyl alcohol. During the addition, the mixture is agitated. The mixture is held, at 150 C. under reduced pressure for a period of 1% hours. At the end of this period, boiling and foaming cease substantially. The resulting product which consists of the mixture of mono-, diand tri-oleyl citrates has an acid value of about 68 and a saponification value of about 242.

Example 6.Shortening composition containing mono-palmityl citrate, di-palmitul citrate, tripalmityl citrate and the mono-alycerides of fatty acid To 5 kilograms of lard are added 150 grams of a mixture oi monoand di-glycerides derived from lard and 50 grams of a mixture of monopalmityl citrate, di-palmityl citrate and tripalmityl citrate. The mixture of monoand diglycerides which contains about 50% of monoglycerides and 50% di-glycerides is produced from the lard in accordance with the method described in Example 1. The mixture oi mono-, diand tri-palmityl citrates which contains about mono-palmityl citrate, about 50% dipalmityl citrate and about 35% tri-palmityl citrate is initially dissolved in a small quantity of the lard, heated to about 60 C. and the resulting solution is added to the main body of lard.

The mixture of mono-, diand tri-palmityl citrates is prepared as follows:

285 grams of anhydrous citric acid are added to 71.5 grams of commercial palmityl alcohol which is previously melted. During the addition, the mixture is agitated. The mixture is held at 150 C. under reduced pressure for a period of 1 hours. At the end of this period, boiling and foaming ceases substantially. The resulting product which consists of a mixture o! 8 mono-. diand tri-palmityl citrates has an acid value or about 92 and a saponiilcation value of about 272.

Lecithin may be added to the shortening compositions prepared in accordance with Examples itofiinamountsoi tolqt.

The term glyceridic oil composition throughout the description and claims denotes any liquid or solid tat which may or may not be specially processed to attain desirable properties, such as plasticity.

The terms and expressions which we have employed are used as terms of description and not of limitation, and we have no intention, in the use of such terms and expressions, of excluding any equivalents of the features described or portions thereof, but recognize that various modifications are possible within the scope of the invention claimed.

What is claimed is:

1. An edible glyceridic oil composition having incorporated therein a mixture or mono-aliphatic, di-aliphatic and tri-aliphatic citrates, in which the aliphatic groups in said citrates have at least 14 carbon atoms and are selected from the class consisting of alkyl groups and alkylene groups, the amounts of said mono-aliphatic, di-aliphatic and tri-aliphatic citrates in said composition being to of mono-aliphatic citrate, to 1 95 of di-aliphatic citrate and to 1 95 of tri-allph'atic citrate.

2. An edible glyceridic oil composition having incorporated therein a mixture of mono-aliphatic,

di-aliphatic and tri-aliphatic citrates, in which the aliphatic groups in said citrates have at least 14 carbon atoms and are selected from the class consisting of alkyl groups and alkylene groups, the amounts of said mono-aliphatic, di-aliphatic and tri-aliphatic citrates in said composition being to of said mono-aliphatic citrate, 1 to 1%% of said di-aiiphatic citrate and V; to 154% of said tri-aliphatic citrate, and 0.002 to 0.1% of a mono-aliphatic ester of citric acid selected from the class consisting of mono-alkyl citrates in which the alkyl group has not more than 12 carbon atoms and mono-alkylene citrates in which the alkylene group has not more than 12 carbon atoms.

3. An edible glyceridic oil composition having incorporated therein a mixture of mono-alkyl, dialkyl and tri-alkyl citrates, in which the alkyl group has at least 16 carbon atoms, the amounts of said mono-alkyl, di-alkyl and tri-alkyl citrates in said composition being 1 to of monoalkyl citrate. to A% of di-alkvl citrate and V; to /2% of tri-alkyl citrate.

4. An edible glyceridic oil composition having incorporated therein a mixture of mono-alkylene, di-alkylene and tri-alkylene citrates, in which the alkylene group has at least 16 carbon atoms, the amounts of said mono-alkylene, di-alkylene and tri-alkylene citrates in said composition having to 54% of mono-alhlene citrate, l; to 56% of di-alkylene citrate and it to /2% 0i trialkylene citrate.

5. An edible glyceridic oil composition having incorporated therein a significant amount of a hydrophilic lipin containing at least one aliphatic hydrocarbon group having from 13 to 21 carbon atoms and a mixture of mono-aliphatic, dialiphatic and tri-aliphstic citrates, in which the aliphatic groups in said citrates have at least 14 carbon atoms and are selected from the class consisting of alkyl groups and alkylene groups, the amounts of said mono-aliphatic, iii-aliphatic and til-aliphatic citrates in said composition being =5 to o1 mono-aliphatic citrate, to 1%?! of di-aliphatic citrate and to 154% of tri-allphatic citrate.

6. An edible glyceridic oil composition having incorporated therein 55 to 254% of aliphatic mono-carboiwlic acid mono-esters of glycerol in which the carboxylic acid residue has at least 14 carbon atoms and a mixture of mono-aliphatic, di-aliphatic and tri-aliphatic citrates, in which the aliphatic groups in said citrates have at least 14 carbon atoms and are selected from the class consisting oi alkyl groups and alkylene groups, the amounts of said mono-aliphatic, di-aliphatic and tri-aliphatic citrates in said composition being a: to 36% of mono-aliphatic citrate, to 1%% of di-aliphatic citrate and Ya to 1%% of trialiphatic citrate;

7. An edible glyceridic oil composition having incorporated therein /2 to 236% of aliphatic mono-carboxylic acid mono-esters of glycerol in which the carboxylic acid residue has at least 14 carbon atoms and a mixture oi mono-aliphatic, di-aliphatic and tri-aliphatic citrates, the amounts of said mono-aliphatic, di-aliphatic and tri-aliphatic citrates in said composition being a: to oi mono-aliphatic citrate, to 1 di-aliphatic citrate and 5 8 to 1 A% of'trialiphatic citrate, the ratio of said mixture of aliphatic citrates to said aliphatic monocarboxylic acid mono-esters oi glycerol being about 2 to 3.

8. An edible glyceridic oil composition having incorporated therein to2%% ofaliphaticmonocarboxylic acid mono-esters of glycerol in which the mono-carboxylic acid residue has at least 14 carbon atoms and a mixture of mono-aliphatic, di-aliphatic and tri-aliphatic citrates, inwhich the aliphatic groups in said citrates have at least 14 carbon atoms and are selected from the class consisting of alkyl groups and alkylene groups, the amounts of said mono-aliphatic, di-aliphatic and tri-aliphatic citrates in said composition being a; to oi mono-aliphatic citrate, to 1 of di-aliphatic citrate and 1 6' to 1%% of trialiphatic citrate, and 0.002 to 0.1% of a monoaliphatic ester of citric acid selected from the class consisting of mono-alkyl citrates in which the alkyl group has not more than 12 carbon atoms and mono-alkylene citrates in which the alkylene group has not more than 12 carbon atoms.

9. An edible glyceridic oil composition havin incorporated therein 1 to 2% of mono-carboxylic acid mono-esters of glycerol in which the carboxylic acid residue has at least 16 carbon atoms and a mixture oi mono-aliphatic, di-aliphatic and tri-aliphatic citrates, in which the aliphatic groups in said citrates have at least 16 carbon atoms and are selected from the class consisting 01 alkyl groups and alkylene groups, the amounts of said mono-aliphatic, di-aliphatic and tri-ali phatic citrates in said composition being to 34% ct mono-aliphatic citrate, 3 to of dialiphatic citrate and to 96 of tri-aliphatic citrate.

10. An edible glyceridic oil composition having incorporated therein 1 to 6% of a mono-hydric alcohol selected from the class consisting of alkyl and alkylene alcohols having at least 14 carbon atoms and a mixture or mono-aliphatic, di-aliphatic and tri-aiiphatic citrates, in which the aliphatic groups in said citrates have at least 14 carbon atoms and are selected from the class consisting 01 alkyl groups and alkyiene groups,

- 10 the amounts of said mono-aliphatic, di-aliphatic and tri-aliphatic citrates in said composition bein a: to of mono-aliphatic citrate, to 1%% of di-aliphatic citrate and to 154% of tri-aliphatic citrate.

11. An edible gLvceridic oil composition having incorporated therein 1 to 8% oi. a mono-hydric alcohol selected from the class consisting oi alkyl and alkylene alcohols having at least 14 carbon atoms, a mixture of mono-aliphatic, (ii-aliphatic and tri-aliphatic citrates. in which the aliphatic groups in said citrates have at least 14 carbon atoms and are selected from the class consisting of alkyl groups and alkylene groups, the amounts of said mono-aliphatic, di-aliphatic and tri-aliphatic citrates in said composition being a, to oi' mono-aliphatic citrate, to 1%% of di-aliphatic citrate and K; to 154% of tri-aliphatic citrate, and 0.002 to 0,196 oi! a mono-aliphatic ester of citric acid selected from the class consisting oi mono-alkyl citrates in which the alkyl group has not more than 12 carbon atoms and mono-alkylene citrates in which the alhlene group has not more than 12 carbon atoms.

12. An edible glyceridic oil composition having incorporated therein 2 to 4% of a mono-hydric alcohol selected from the class consisting oi. alkyl and alkylene alcohols having at least 16 carbon atoms and a mixture 01' mono-aliphatic, di-aliphatic and tri-aliphatic citrates, in which the aliphatic groups in said citrates have at least 16 carbon atoms and are selected from the class consisting 01' alkyl groups and alkylene groups. the amounts of said mono-aliphatic, di-aliphatic and tri-aliphatic citrates in said composition being 1*; to of mono-aliphatic citrate, 54; to b of (ii-aliphatic citrate and to of tri-aliphatic citrate. I

13. An edible glyceridic oil composition having incorporated therein $4; to 1%% oi. aliphatic mono-carboxylic acid mono-esters of glycerol in which the carboxylic acid residue has at least 14 carbon atoms, V to 3% of a mono-hydric alcohol selected from the class consisting of alkyl and aikylene alcohols having at least 14 carbon atoms and a mixture of mono-aliphatic, di-aliphatic and tri-aliphatic citrates, in which the aliphatic groups in said citrates have at least 14 carbon atoms and are selected from the class consisting oi alkyl groups and alkylene groups, the amounts of said mono-aliphatic, di-aliphatic and tri-aliphatic citrates in said composition being to oi mono-aliphatic citrate, to 1%% of dialiphatic citrate and to 1 of tri-aliphatic citrate.

14. The method oi producing an edible glyceridic oil composition which comprises incorporating in an edible glyceridic oil a mixture of a mono-aliphatic citrate, a di-aliphatic citrate and a tri-aliphatic citrate in which the aliphatic groups in said citrate have at least 14 carbon atoms and are selected from the class consisting of aliryl groups and alkylene groups, the amount of said mono-aliphatic, di-aliphatic and tri-aliphatic citrates incorporated in said oil being a! to oi mono-aliphatic citrate, to 1%% of di-aliphatic citrate, and $4; to 1%95 oi tri-aliphatic citrate.

15. The method oi producing an edible glyceridic oil composition which comprises incorporating in an edible glyceridic oil a significant amount of a hydrophilic lipin containing at least one aliphatic hydrocarbon group having at least 13 carbon atoms and a mixture of a mono-aliphatic citrate, a di-aliphatic citrate and a tri- 11 aliphatic citrate, in which the aliphatic groups in said citrates have at least 14 carbon atoms and are selected from the class consisting of alkyl and alkyiene groups, the amount of said mono aliphatic, di-aliphatic and tri-aliphatic citrates 6 incorporated in said oil being a: to of monoaliphatic citrate. 1; to 1 ,596 of di-aliphatic citrate, and $4, to 1 96 of tri-aliphatic citrate.

16. The method of producing an edible glyceridic oil composition which comprises incorporating in an edible gLYceridic oil a significant amount of alphatic mono-carboxylic acid mono esters of glycerol in which the carboxylic acid residue has at least 14 carbon atoms, and a mixture of a mono-aliphatic citrate, a di-aliphatic citrate and a tri-aliphatic citrate, in which the aliphatic groups in said citrates have at least 14 carbon atoms and are selected from the class consisting of alkyl and allwlene groups, the amount of said mono-aliphatic, (ii-aliphatic and h-i-aliphatic citrates incorporated in said oil being to 35% of mono-aliphatic citrate, 1 to 1 96 of di-aliphatic citrate, and $4; to 1%% of tri-aliphatic citrate.

HANS w. VAHL'I'EICH. CHESTER M. GOODING.

E'I'HELN'EAL,

Administratrix of the Estate 0] Ralph H. Neal,

Deceased.

REFERENCES crran The following references are of record in the file of this patent:

UNITED STATES PATENTS garine Mi'g., Washington 4, D.'C., April 1944, page 2.

Number Certificate of Correction Patent No. 2,485,639

HANS W. VAHLTEICH ET AL.

It is hereby certified that errors appear in the printed specification of the above numbered patent requiring correction as follows:

Column 4, line 5, for "phophatides read pho hat'ides; column 7, line 1, for "trim-myristyl read tr'i-myristyl; column 10, line 36, or X to )4 read X to and that the said Letters Patent should be read with these corrections therein that the same may conform to the recordof the case in the Patent Office.

Signed and sealed this 25th day of April, A. D. 1950.

THOMAS F. MURPHY,

Assistant Oommim'oner of Patents.

October 25, 1949 V 

